Production of colored photographic layers



Patented Jan. 9, 1940 UNITE PRODUCTION OF COLORED PHOTOGBAPHIC LAYERS ofDelaware No Drawing.

Application May 22, 1937, Serial No. 144,309. In Germany May 23, 1936 17Claims.

This invention relates to photographic material.

One of its objects is toprovide a photographic material for colorphotography. Further objects will be seen from the detailed,specification following hereafter.

The methods hitherto known for fixing dyestufis in colloid layersconsist in either utilizing the substantive character of an azo-dyestuffto fix it in gelatin or producing an insoluble azodyestufl' in thegelatin. It is also possible to produce indophenols in fine dispersionin a colloid layer or to introduce into the layer the dyestufi in avatted condition and subsequently to oxidize it. These processes havethe disadvantage that, for example, the substantive azo-dyestuffsdiffuse very strongly even at high concentration, while the use of someof the methods-involves incorporation in the colloid of a-solvent orproductof reaction which must subsequently be washed out and in manycases gives rise to damage, as for instance in photographic layers.

This invention is based on the observation that these dyestufis may bemade fast to diffusion if there is introduced into the dyestuif moleculean alkyl residue of high molecular .weight and that the fastness todiffusion thus produced does not suffer if a sulfuric acid group, orother group lending solubility in water, is introduced.

In U. S. Patent application Ser. No. 94,340 filed Aug. 5, 1936, there isdescribed acolor photograph process in which the dyestuff intermediateproduct is made fast to diffusion in colloids by the introduction of analkyl residue having more than 5 carbon atoms. The present inventionextends this idea to those photographic materials which contain finisheddyestuffs. Such-dyestuffs may be made, for example, by treating thedyestufi containing one or more amino groups with a fatty acid chlorideor treating an acid chloride of the dyestufi with a fatty amine.Alternatively, the dyestufi may contain originally an alkyl residue ofhigh molecular weight, for example an alkylated benzene ring or analkylated naphthol ring. The invention is not limited to any specificclass of dyestuffs, but is applicable to all classes of dyes. Forinstance an azo-dyestuff according to the present invention may beprepared by diazotizing an alkyl aniline in which the alkyl radical hasa. long aliphatic carbon chain, and coupling said diazotized anilinewith a phenolor napthol-sulfonic acid.

The dyestufl's are used for instance for multicolor photography andparticularly for multilayer material comprising superimposed layers;also for anti-halation layers and filter layers and for screen covers.When the dyestuffs are introduced into colloids suitable as bindingagents, there are formed layers which, on account of their fastness todiffusion, are particularly suitable as filter layers, screening layersand anti-halation layers in the construction of a multi-layer material.They are particularly useful as such layers in combination with those ofthe aforesaid U. S. patent application for making a material formulti-color photography.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto (1) A red, bluish dyestufi which isparticularly suitable as a filter dyestufi or multi-color material ismade by coupling oleyl-H-acid with diazotized sulfanilic acid. I

(2 A yellow dyestufl of the'following composition:

Nncoomnn CO H iri som.

and made as described in U. S. Patent 2,036,546, is particularlysuitable for anti-halation purposes.

(3) Another yellow dyestufl corresponding with the formula V HaC SOLCH;

HasCmCQNH -ocm cm some,

(5) The condensation product from G-aminoquinaldine dimethyisuliateandp-dimethylaminobenzaldehyde is reacted with undecoylchloride in thepresence of organic bases. The resulting red dyestuff corresponds withthe formula (6) The condensation product from1.2.3.3-tetramethyl-5-methoxy-indoleninium acetate ando-amino-benzaldehyde is reacted with capric acid chloride in the mannerdescribed in Example 5. The resulting orange dyestufi corresponds withthe formula (7) The condensation product fromZ-methylthiazoline-dimethyl-sulfate and p-amino-benzaldehyde is reactedwith undecylenic acid chloride in a manner described in Example 5. Theresulting light yellow dyestufi corresponds with the formula I Hat:('JCH=CHONH.C 0.0mm

02m .GH=CHONH.C 0.010%

C 3 SO .CH3

(9) The condensation product from 2-methyl-4-phenylthiazole-dimethylsulfatel and 4-aminobenzaldehyde-B-sulfonicacid is reacted with ricinoleic acid chloride in the manner describedabove. The resulting light yellow dyestuif corresponds with the formulal CH3 504.0113

S OaH (l)1(3'-amino-5'-sulfo)-phenyl 3-methyl- -pyrazolone is condensedwith stearic acid chloride and is coupled with p-dimethylamino-anilinein the presence of an oxidizing agent. As an oxidizing agent, forinstance, potassium ferricyanide in an alkaline solution may be used.The

resulting red dyestuff corresponds with the formula (11)5-amino-a-naphthol 'is reacted with stearic acid chloride, the resultingproduct is sulfonated and coupled with p-diethyl-amlno-aniline in thepresence of an oxidizing agent. The resulting blue dyestufi correspondswith the formula "Has What I claim is:

1. A photographic element comprising at least one silver halide emulsionlayer, a colored filter layer in contact with said silver halideemulsion layer, said filter layer containing a dyestufl which is fast todiffusion with respect to the binding agent of said layer, said dyestuffhaving an alkyl radical of a carbon chain of more than 5 carbon atomslinked to an atom of its molecule by a linkage selected from the groupconsisting of the acid amide-, ester-, and direct carbon to carbonlinkage.

2. A photographic element comprising at least one silver halide emulsionlayer, a colored filter layer in contact with said silver'halideemulsion layer, said filter layer containing a dyestufl which is fast todiffusion with respect to the binding agent of said layer, said dyestuiThaving an aliphatic acyl radical having a carbon chain of more than 5carbon atoms linked to an amino group of the dyestuff molecule.

3. A photographic element comprising at least one silver halide emulsionlayer, a colored filter layer in contact with said silver halideemulsion layer, said filter layer containing a dyestuff which is fast todiffusion with respect to the binding agent of said layer, said dyestuffhaving an alkyl amino radical with a carbon chain of more than 5 carbonatoms linked to a carboxylic acid group of the dyestufl molecule.

4. A photographic element comprising at least one silver halide emulsionlayer, a colored filter layer in contact with said silver halideemulsion layer, said filter layer containing a dyestuff which is fast todiffusion with respect to the binding agent of said layer, said dyestuifhaving an alkyl radical of a carbon chain of to 18 carbon atoms linkedto an atom of its molecule by a linkage selected from the groupconsisting of the acid amide-, ester-, and direct carbon to carbonlinkage.

5. A photographic element comprising at least one silver halide emulsionlayer, a colored filter layer in contact with said silver halideemulsion layer, said filter layer containing a dyestufi which is fast todiffusion with respect to the binding agent of said layer, saiddyestufl. having an aliphatic acyl radical having a carbon chain of 10to 18 carbon atoms linked to an amino group of the dyestufi molecule,

6. A photographic element comprising at least one silver halide emulsionlayer, a colored filter layer in contact with said silver halideemulsion layer, said filter layer containing a dyestuff which is fast todiffusion with respect to the binding agentof said layer, said dyestufihaving an alkyl amino radical with a carbon chain of 10 to 18 carbonatoms linked to a carboxylic acid group of the dyestufi molecule.

'7. A photographic element comprising at least one silver halideemulsion layer, a colored filter layer in contact with said silverhalide emulsion layer, said filter layer containing a dyestuff which isfast to diffusion with respect to the binding agent of said layer, saiddyestufi having an alkyl radical of a carbon chain of more than 5 carbonatoms linked to an atom of its molecule by a homopolar linkage.

8. A photographic element comprising at least one silver halide emulsionlayer, a colored filter layer in contact with said silver halideemulsion layer, said filter layer containing a dyestuff which is fast todiffusion with respect to the binding agent of said layer, said dyestuifhaving an alkyl radical of a carbon chain of 10 to 18 carbon atomslinked to an atom of its molecule by a homopolar linkage.

9. The photographic element defined in claim 1, wherein said dyestuff isan azo dyestufi.

10. The photographic element defined in claim 1, wherein said dyestufiis a styryl dyestuif.

11. The photographic element defined in claim 1, wherein said dyestufiis a styryl dyestuff and in which the heterocyclic nucleus thereof isselected from the class consisting of a benzthiazole, benzoxazole,quinoline, indoline and thiazole nucleus.

12. The photographic element defined in claim 1, wherein the dyestuff isa styryl dyestuif in which the heterocyclic nucleus thereof is selectedfrom the class consisting of a benzthiazole. benzoxazole, quinoline,indoline and thiazole nucleus, said alkyl radical being linked to acarbon atom of the benzo ring of the heterocyclic nucleus by an acidamide linkage.

13. The photographic element defined in claim 1, wherein said dyestuflis produced by coupling in the presence of an oxidizing agent ap-dialkylamino-aniline with a condensation product of a compoundselected from the group consisting of an amino-pyrazolone and anamino-naphthol with a fatty acid having from 10 to 18 carbon atoms.

14. A photographic element comprising at least one silver halideemulsion layer, a colored filter layer in contact with said silverhalide emulsion nCmCOllN CH: SO4.CH$

16. A photographic element comprising at least onesilver halide emulsionlayer, a colored filter layer in contact with said silver halideemulsion layer, said filter layer containing a dyestuff which is fast todifiusion with respect to the binding agent of said layer, said dyestuifhaving the following formula:

C11Hu.CO.HN SOzNa 1'7. A photographic element comprising at least threecontacting layers in super-position, one layer being a base, at leastone layer being a silver halide emulsion layer and one layer being acolored colloidal light-absorbing layer containing a dyestufi which isfast to diffusion with respect to the colloid of said layer, saiddyestufi having an alkyl radicle of a carbon chain of more than 5 carbonatoms linked to an atom of its molecule by a homopolar linkage.

SCHNEIDER.

